Functionalized fluoropolyethers

ABSTRACT

Fluoropolyethers having functional groups, consisting of randomly distributed sequences of perfluoropolyoxyalkylene units selected from: ##STR1## and included in one of the following formulas: ##STR2## 
     
         T&#39;--O--(CF.sub.2 CF.sub.2 O).sub.p (CF.sub.2 O).sub.s --CRR&#39;--Y(II) 
    
      ##STR3## where X is F or CF 3  T, T&#39;, T&#34;=a perfluoroalkyl group containing from 1 to 3 carbon atoms and one or two atoms of Cl, Br or I; 
     R, R&#39;=halogen atoms; 
     Y=a functional group; 
     o, q=numbers, zero included, such that o+q=1-20; 
     n=a number ranging from 1 to 15; 
     m/n=a number ranging from 0.01 to 0.5; 
     p=a number ranging from 1 to 20; 
     s/p=a number ranging from 0.5 to 2; and 
     z/o+p=a number ranging from 0.01 to 0.05.

This is a divisional of application Ser. No. 08/209,497 filed on Feb.24, 1994, now U.S. Pat. No. 5,446,205; which is a continuationapplication of Ser. No. 07/872,209 filed on Apr. 22, 1992; which is acontinuation application of Ser. No. 07/727,309 filed on Jul. 10, 1991;which is a continuation application of Ser. No. 07/614,551 filed on Nov.15, 1990; which is a continuation application of Ser. No. 07/346,480filed on May 2, 1989.

DESCRIPTION OF THE INVENTION

The present invention relates to functionalized fluoropolyethersconsisting of randomly distributed sequences of perfluorooxyalkyleneunits selected from: ##STR4## --CF₂ --CF₂ --O--; --CF₂ O--; ##STR5## andhaving a functional end group Y, the other end group being aperhaloalkyl group containing one or two atoms of a halogen other thanfluorine, such fluoropolyethers being included in the following formulas(I), (II) and (III): ##STR6## where: X is F or CF₃ ;

R is F or Cl or Br or I;

R', equal to or different from R, is also F or Cl or Br or I;

T is a perhaloalkyl group containing from one to three carbon atoms andone or two atoms of Cl or Br or I; in particular, T may be: ##STR7##where Alog is Cl or Br or I;

n ranges from 1 to 15, with m/n being between 0.01 and 0.5;

Y may be a --CN or --CH₂ Z or --COR'" group, or: ##STR8## where: E maybe NH, or an atom of O or S, and furthermore:

(A) when Y=--CH₂ Z, Z may be a group OR", where R" may be a hydrogenatom, or a group: ##STR9## where b is a number ranging from 1 to 15;##STR10## (c=a number from 1 to 3); ##STR11## where R₁ =and alkylcontaining from 1 to 30 carbon atoms, and optionally containing etherealbonds of the type --C--O--C--, or R₁ is a group --(CH₂ CH₂ O)_(d) Hwhere n is a number between 1 and 15; ##STR12## and furthermore anaphthyl group, a benzl group or a mono- or poly-substituted alkyl oralkoxy benzyl group of the type: ##STR13## where R₂ --an alkylcontaining from 1 to 4 carbon atoms said alkyl and alkoxy benzyl groupoptionally containing one or more substituents; or

Z may be a nitrogen-containing group --NR₃ R₄ ; where R₃ and R₄, alikeor different from each other, may be hydrogen atoms or they may be,either individually or both, R₁ groups as defined above, or, when R₃ =H,R₄ may be a group: ##STR14## or R₃ and R₄ together may form a cyclicimide of formula: ##STR15## wherein the phenyl group may contain asubstituting group of the anhydride type; ##STR16## (B) when Y=a COR'"group, R'" may be an --NHR₅ group, where R₅ may be hydrogen or alkylwith 1 to 8 carbon atoms, or R₅ may be a mono- or poly-hydroxyalkyl with1 to 8 carbon atoms, an aminoalkyl with 1 to 8 carbon atoms, an allygroup, a methallyl group, a trimethoxy- or triethoxy-silanealkyl groupof formula: R₆ --Si(OCH₃)₃ or R₆ Si(OC₂ H₅)₃, where R₆ =an alkylene with1 to 8 carbon atoms, or an isocyano alkyl of formula R₆ NCO, or anisocyanocycloalkyl group with 5 to 6 carbon atoms, or an isocyano arylgroup with 6 to 10 carbon atoms, optionally alkyl-substituted; or R'"may be an aromatic radical optionally alkyl- or halogen-substituted suchas, for example: pentafluorophenyl, bromotetrafluoro-phenyl,dibromodifluorophenyl, bromophenyl, bromo-benzophenyl,

    T'≠O(CF.sub.2 CF.sub.2 O).sub.p (CF.sub.2)).sub.s CRR' Y(II)

where:

T'=Alog CF₂ CF₂ --; Alog CF₂ --; Alog CF₂ CF(Alog)--;

R, R' Alog, Y are the same as defined above for formula (I);

p ranging from 1 to 20, and s/p from 0.5 to 2. ##STR17## where: Y, X, Rand R' are the same as defined above for formula (I),

T" is equal to T or T', o and q are numbers, zero included, o+q=1-20,z/o+q ranging from 0.01 to 0.05.

The products of the present invention may be prepared starting fromfluoropolyethers consisting of randomly distributed sequences ofperfluorooxyalkylene units selected from: ##STR18## and included in thefollowing formulas: ##STR19## where: X is F or CF₃ ;

R is F or Cl or Br or I;

R' like or different from R, is also F or Cl or Br or I; ##STR20## withR being the same as defined above, or L is the corresponding --COOHgroup or a salt or an ester thereof;

T is a perhaloalkyl group containing from 1 to 3 carbon atoms and one ortwo atoms of Cl or Br or I: in particular T may be Alog CF₂ --, Alog CF₂--, ##STR21## Alog CF₂ CF(CF₃)%-- where Alog is Cl or Br or I;

n ranges from 1 to 15, and m/n ranges from 0.01 to 0.5;

    T'--O (CF.sub.2 CF.sub.2 O).sub.p (CF.sub.2 O).sub.s CRR'--L(II)

where:

T'=Alog CF₂ CF₂ --;

Alog CF₂ --;

Alog CF₂ CF(Alog)

L, R, R', Alog are the same as defined above for formula (I), p rangesfrom 1 to 20, s/p ranges from 0.5 to 2. ##STR22## where: L, X, R and R'are the same as defined above for formula (I),

T" is equal to T or T', o and q are numbers, zero included, o+q=1-20,z/o+q=from 0.01 to 0.05.

In particular, the following cases are possible:

1) Y=--COR'".

In such case, the possibilities are as follows:

(a) R'"=NHR₅ group. In this case, the products are of the amidic type.They are preparable by reacting ammonia or amines of formula NH₂ R₅ Withthe corresponding alkyl esters, if the amines are strongly basic, orwith the corresponding phenyl esters or the corresponding acylhalides,if the amines are weakly basic or highly sterically hindered. Separationand purification of the products are carried out by conventionaltechniques. Another method comprises reacting the fluoropolyether havingthe acid end group --COOH with compounds containing --NCO(isocyanate)groups at temperatures ranging from 100° to 120° C., with CO₂generation.

(b) R'"=an optionally substituted aromatic radical. In this case it is aquestion of ketonic products, which are preparable by means of theFriedel-Craft reaction between the corresponding aromatic compound andthe perfluoropolyether containing the acyl group --COCl, or by means ofreaction between lithium-aromatic derivatives and perfluoropolyethershaving an ester end group.

2) Y'=CH₂ Z

In this case the possibilities are as follows:

(a) Z=OR". In this case, the products are obtainable from thecorresponding carboxylic (or ester) starting products by reduction ofthe group --C-- with Li, Na, B, Al complex hydrides. O Usually, theorigin product is the alcoholic derivative --CH₂ OH. The subsequentderivatives are preparable by nucleofilic reaction of the alcoholatewith compounds of formula R"X where X is a movable halogen, generallychlorine, or by addition of the alcoholate to epoxy cyclic compounds.For example: when R"=a group ##STR23## it is possible to operate byreaction of the Na or K alcoholates with epichlorohydrin in excess;after having removed the epichlorohydrin excess, neutralization iscautiously carried out under cold conditions and glycidyl ether isseparated by extraction and, if necessary, by distillation; when R"--agroup ##STR24## it is possible to operate by reaction of alcohols --CH₂OH in the presence of alcoholate traces (as a catalyst) on glycidylalcohol at 60°-80° C., then by acidification and separation of thepolyhydroxy derivative; when R"=a --CH₂ COOR group it is possible tooperate by reaction of the Na or K alcoholate on ethyl chloroacetate inan ether-solvent; the product is obtained after repeatedly washing theorganic phase with water, optionally enriched with FC 113(1,1,2-trichloro-1,2,2-trifluoroethane); when R"=a ##STR25## group it ispossible to operate by reaction of the alcohols with acrylylchloride inan ether solvent in the presence of tertiary bases; when R"=a --(CH₂ CH₂O)_(d) H group it is possible to operate by reaction of the alcohols inthe presence of catalytic amounts of alcoholates with ethylene oxide attemperatures around 100° C.; when R"=a group ##STR26## it is possible tooperate by reaction of the alcoholates with the chloromethyl aromaticderivatives in inert solvents; when R" is a --CH₂ --CH═CH₂ group, it ispossible to operate by the reaction of the alcoholates with allylchloride or bromide under such conditions as to cause the precipitationof the alkaline chlorides or bromides, and by extration of theallyl-ethers. For functional groups which are farther away from theperfluoropolyether chain, the reactions already known in organicchemistry are utilizable, as in such position there is no longer anyinfluence of the fluoroether group.

(b) Z=--NR₃ ₄. When Z=--NR₃ R₄, the products are preparable byreduction, according to conventional methods, of the correspondingamidic derivatives when R₃ and R₄ do not contain reducible groups. Inthe contrary case, the products are obtained from the correspondingperfluoropolyethers containing end group ##STR27## prepared as mentionedabove, by reduction with the above-cited hydrides, and by subsequentreaction of one or two hydrogen atoms of the --NH₂ group with R₄ Xcompounds (X=halogen), or, when R₃ and R₄ form a cyclic imide, by directreaction of the --NH₂ group with a cyclic anhydride: ##STR28## carriedout in polar aprotic solvents, or in bulk at high temperatures(150°-200° C.).

(3) When Y=CN, the products are obtained by dehydration with P₂ O₅, attemperatures from 100° to 200° C., of the --CONH₂ group of thecorresponding amidic derivative.

The fluoropolyethers having an acid functional end group to be used asstarting products for preparing the compounds of the present invention,may be prepared by photooxidation of perfluoropropene and/ortetrafluoroethylene in the presence of minor amounts of a fullyhalogenated ethylene containing fluorine and at least one atom of ahalogen other than fluorine. The photooxidation product is thenthermally treated to remove the peroxide groups contained therein.

Such fluoropolyethers and the process for preparing them are describedin the commonly-owned Italian patent application No. 20,406 A/88, thecontent of which is incorporated herein by reference.

As regards utilization, in the first place, it is used as a fluorinatedsurfactant in the form of a salified monocarboxylic acid (ammonium saltor alkali metal salt), or in the protection of monuments and of stonymaterials in general against atmospheric agents. The functionalizedfluoropolyethers of the present invention are particularly capable ofreacting with organic and inorganic substrates, as well as with endgroups containing 1 or 2 atoms of a halogen different from fluorine.They are used as surface modifiers for polymeric and inorganicmaterials, in order to impart properties which are typical offluorinated products such as water- and oil-repellency, low coefficientsof friction, low refractive index, and the like.

The following examples are given still better to illustrate the presentinvention, but they are not to be construed as a limitation thereof.

EXAMPLE 1

17 g of a mixture of acids of formula:

    Cl C.sub.3 F.sub.6 O(C.sub.3 F.sub.6 O).sub.n (CF.sub.2 O).sub.m CF.sub.2 COOH

prepared according to the procedures described in Examples 1 through 6of Italian patent application No. 20,406 A/88, where n has an averagevalue of 0.85 and M has an average value of 0.02, were mixed with 6g ofP₂ O₅, and the resulting mixture was heated from 100° to 200° C. in aglass flask having, superposed thereon, a Vigreux column (8×150 mm) anda Liebig cooler. There were thus obtained 12 g of a liquid distillingfrom 170° absorptions at 1805-1870 cm⁻¹ characteristic of carbonylgroups, and by the absence of bands attributable to hydroxyls in theregion from 3300 to 3600 cm⁻¹. Thus, the structure of an anhydride offormula:

    (Cl C.sub.3 F.sub.6 O(C.sub.3 F.sub.6 O)0.85(CF.sub.2 O)0.02CF.sub.2 CO).sub.2 O

is attributable to the compound.

14 g of the same acid were reacted with 10 cc of thionyl chloride for 8hours under reflux, in the presence of 0.1 g of pyridine. Afterreaction, most of the thionyl chloride was distilled off, then theresulting concentrate was distilled, thereby obtaining, from 105° to120° C. (at 760 mm Hg), 9 g of a product characterized, on infraredanalysis, by a marked absorption at 1805 cm⁻¹ and by the absence ofabsorptions from 3300 to 3600 cm⁻¹. On the basis of the percent contentof hydrolyzable chlorine (with aqueous NaOH 0.5 N), the formula:

    Cl(C.sub.3 F.sub.6 O(C.sub.3 F.sub.6 O)0.85(CF.sub.2 O)0.02CF.sub.2 COCl

was attributed to the product.

7 g of such product, mixed with 1.5 g of anhydrous benzene, were addedto a suspension of 3.5 g of AlCl₃ in 15 cc of CH₂ Cl₂, cooled to 0° C.,and maintained under stirring. During the reaction, the mixture turnedred and became homogeneous; after a 4-hour reaction, the mixture waspoured into iced water, and the demixed organic phase was collected,washed with water and bicarbonate, dried on Na₂ SO₄ concentrated by CH₂Cl₂ and distilled, thereby obtaining, at 195°-198° C., a compound (3 g)characterized, in the infrared spectrum, by absorption bands at 1720cm⁻¹ characteristic of a carbonyl and at 1500 and 1600 cm⁻¹characteristic of the benzene ring, wherefore the structure:

    Cl C.sub.3 F.sub.6 O(:C.sub.3 F.sub.6 O)0.85(CF.sub.2 O)0.02CF.sub.2 COC.sub.5 H.sub.5

was attributed to the product.

EXAMPLE 2

90 g of a mixture of acids of formula:

    Cl C.sub.3 F.sub.6 O(C.sub.3 F.sub.6 O).sub.n (CF.sub.2 O).sub.m CF.sub.2 COOH

prepared as in Example 1, where n has an average value of 1.27 and m isequal to 0.05, were reacted with 100 g of ethanol at 99.9% in thepresence of 2 g of H₂ SO₄ at 96% and 60 g of benzene, in a 250 cc flask,with a rectification column (1×100 cm) packed with Helipack superposedthereon. The temperature was maintained at such level as to keep themixture boiling. For 3 hours no distillate was withdrawn, then, with areflux ratio of about 20, the azeotrope (water, benzene, ethanol=43 ml)was collected on the top in 6 hours; then, by reducing the reflux ratioto 5, most of the benzene-ethanol azeotrope (140 ml) was allowed todistill. At the end, the obtained product was poured into iced water andimmediately separated, whereafter it was dried on Na₂ SO₄ and distilled,thereby collecting, at 170°-180° C., 82 g of product.

On infrared analysis, such product no longer exhibited the bands whichare typical of the acid, and it could not be titrated with a solution oftriethylamine in methanol, contrary to the starting mixture of acids.

The N.M.R. analysis evidenced the presence of the ester group: ##STR29##

43 g of the ethyl ester so obtained were dissolved in 150 cc of ethylether cooled to 0° C. and a gaseous ammonia flow was conveyed for 2hours to the solution. During such period of time the reaction wascompleted. After evaporation of the ether, the remained liquid wasrectified, so that it was possible to collect, between 240° and 260° C.,a product, which, on infrared analysis, was characterized by absorptionsat 1740 cm⁻¹ and 1610 cm⁻¹.

    Cl C.sub.3 F.sub.6 O(C.sub.3 F.sub.6 O).sub.1.27 (CF.sub.2 O).sub.0.05 CF.sub.2 CONH.sub.2

was attributable.

14 g of the above-mentioned ethyl ester were dissolved in 10 cc of ethylether and were addtioned with 2.4 cc of n-butylamine.

The mixture was reacted for 1 hour, then the solvent was concentratedand distillation was carried out, thereby collecting, between 220° and230° C., a product which, on elemental analysis (C=34.4%, Cl=7.9%,F=40.5%, H=2%) and on infrared and N.M.R. ¹⁹ F analyses, was shown to bethe amide of structure:

    Cl (C.sub.3 F.sub.6 O(C.sub.3 F.sub.6 O).sub.1.27 (CF.sub.2 O).sub.0.05 CF.sub.2 CONHC.sub.4 H.sub.9.

EXAMPLE 3

9.4 g of the amide of formula:

    Cl C.sub.3 F.sub.6 O(C.sub.3 F.sub.6 O).sub.1.27 (CF.sub.2 O).sub.0.05 --CF.sub.2 CONH.sub.2

of the preceding example were mixed in a glass flask, equiped with acooler, with 20 g of P₂ O₅ and the resulting mixture was heated for 2hours at 150°-180° C. After having removed the cooler the thus obtainedliquid product was distilled, which was then distilled again, therebycollecting 7 g of fraction boiling between 120° and 130° C.

The product of that fraction is characterized, on infrared analysis, bya sharp absorption band at 2250 cm⁻¹, which is typical of the --CNgroup, wherefore the formula of the nitrile:

    Cl C.sub.3 F.sub.6 O(C.sub.3 F.sub.6 O).sub.1.27 (CF.sub.2 O).sub.0.05 CF.sub.2 CN

is attributed to the product.

EXAMPLE 4

A sample (20 g) of phenyl ester of formula:

    Cl C.sub.3 F.sub.6 O(C.sub.3 F.sub.6 O).sub.1.27 (CF.sub.2 O).sub.0.05 CF.sub.2 COOC.sub.6 H.sub.5

prepared, starting from 10 cc of the acid described in Example 2, byreactions of conversion to the corresponding acyl chloride andsubsequent reaction with phenol in the presence of pyridine and washingwith an agueous alcoholic solution, was reacted with 3.7 g of0-phenylenediamine by gradually heating from 30° to 200° C. carried outin 20 hours. The product obtained was a green solid, having a meltingtemperature of 65°-70° C. and a boiling temperature of 230°-260° C., andwas characterized by sharp absorption bands in the infrared spectrum, at1450, 1490, 1540, 1590 cm⁻¹ (relevant to condensed rings and to grouping--C═N-- in the ring), as well as by a broad absorption in the areabetween 2700 and 3100 cm⁻¹ due to C--H and N--H bonds.

Elemental analysis (C=32.5%, Cl=6.4%, H=0.1%, F=54.9%) confirmed thatthe product had the following structure: ##STR30##

EXAMPLE 5

10 g of the nitrile of Example 3 were reacted in a glass vial at atemperature of -50° C. with anhydrous ammonia in excess. The excessammonia was removed from the product, to which the structure of thecorresponding amidine of formula: ##STR31## was attributed on the basisof the typical infrared absorption bands at 1600 cm⁻¹ characteristic ofthe iminic group, and in the area between 3400-3100 cm⁻¹, characteristicof N--H bonds.

A sample (5 g) of the amidine so obtained, after gradually heating up to300° C. in 8 hours until the conclusion of evolution of ammonia, wasthereby converted to a highly viscous liquid characterized, on infraredanalysis, by a single sharp absorption band at 1550 cm⁻¹, correspondingto the --C═N-- group of the triazine ring, wherefore the structure ofsimpolyoxachloroperfluoroalkyltriazine of formula ##STR32## where R_(f)=the radical ClC₃ F₆ O(C₃ F₆ O)₁.27 (CF₂))₀.05 --CF₂)-- is attributableto the compound.

EXAMPLE 6

50 g of ethyl ester:

    ClC.sub.3 F.sub.6 O(C.sub.3 F.sub.6 O).sub.1.27 (CF.sub.2 O).sub.0.05 CF.sub.2 COOC.sub.2 H.sub.5

according to Example 2, were added in 2 hours to a suspension of 4 g ofLiAlH₄ in 250 cc of anhydrous ethyl ether, at a temperature ranging fromroom temperature to 35° C. After a 3-hour reaction, the excess of LiAlH₄was decomposed with HCl at 5%, the ether phase was separated, dried withNa₂ SO₄, concentrated and then distilled at atmospheric pressure,whereafter the fraction of product boiling from 150° to 170° C. wascollected.

On infrared analysis, this product no longer exhibited the absorptionbands attributable to carbonyl, but a broad band attributable to thehydroxyls. By treatment with a weighed amount of acetic anhydride, inthe presence of pyridine and ethyl ether, after 12 hours, by hydrolyzingthe excess of anhydride, acetic acid was countertitrated and for suchproduct an equivalent molecular weight of 490, referred to hydroxyls,was obtained.

NMR(¹ H) analysis confirmed the following structure of the product:

    ClC.sub.3 F.sub.6 O(C.sub.3 F.sub.6 O).sub.1.27 (CF.sub.2 O).sub.0.05 CF.sub.2 CH.sub.2 OH.

EXAMPLE 7

55 g of amide:

    ClC.sub.3 F.sub.6 O(C.sub.3 F.sub.6 O).sub.1.27 (CF.sub.2 O).sub.0.05 CF.sub.2 CONH.sub.2

prepared according to Example 3 were added, in 2 hours, to a suspensionof 4 g of LiAlH₄ in 300 cc of ethyl ether at room temperature.

After a 2-hour reaction at room temperature and a 2-hour reaction at 35°C. the excess of LiAlH₄ was decomposed at 0° C. with an aqueous solutionof tetrahydrofuran, whereafter 500 g of H₂ O and 50 cc of aqueous NaOHat 40% were added to the mixture.

The organic layer was separated, dried on Na₂ SO₄ and distilled: thefraction boiling between 140° and 160° C. (40 g) was collected.

The infrared analysis no longer revealed absorption bands attributableto carbonyl groups.

The structure:

    ClC.sub.3 F.sub.6 O(C.sub.3 F.sub.6 O).sub.1.27 (CF.sub.2 O).sub.0.05 CF.sub.2 CH.sub.2 NH.sub.2

was attributable to the product.

The aminic equivalent weight, determined by titration with HClO₄ (0.1Nin acetic acid), was equal to 495.

EXAMPLE 8

A solution of 1.6 cc of acrylyl chloride in 20 cc of ethyl ether wasadded to a solution of 11 g of an amine of formula:

    ClC.sub.3 F.sub.6 O(C.sub.3 F.sub.6 O).sub.1.98 (CF.sub.2 O).sub.0.08 CF.sub.2 CH.sub.2 NH.sub.2

prepared according to the method of Example 7, starting from the amideof the corresponding acid, and 2.8 cc of triethylamine in 100 cc ofethyl ether cooled to 0° C. and maintained under stirring. The mixturewas reacted for 3 hours at 0° C. after which it was filtered.

The ethereal solution so obtained was additioned with 0.1 g ofphenothiazine ##STR33## then it was concentrated and distilled: 7 g ofthe fraction of product were collected from 105° to 115° C. under apressure of 15 mm Hg. Such product was characterized by absorption bandsin the infrared spectrum, at 1730 cm⁻¹, attributable to carbonyl, and at1625 cm⁻¹, attributable to the double bond.

The structure of an acrylamide of formula:

    ClC.sub.3 F.sub.6 O(C.sub.3 F.sub.6 O).sub.1.98 ═(CF.sub.2 O).sub.0.08 --CF.sub.2 --CH.sub.2 NHCO--CH═CH.sub.2

was attributable to the product.

The NMR (¹ H) analysis also confirmed the above-indicated structure.

EXAMPLE 9

A mixture of acids of formula

    TO(C.sub.2 F.sub.4 O).sub.n (CF.sub.2 O).sub.m CF.sub.2 COOH

obtained according to the procedure of Examples 9 to 19 of Italianpatent application No. 20,406 A/88, where: T=ClCF₂ or Cl CF₂ CF₂,m/n=1.2 with a molar ratio: --COOH/T=1.1, and having an averagemolecular weight equal to 900, was esterified as described in Example 2.

After removal of the alcoholic phase, the layer consisting of the ethylesters of the perfluorinated acids was purified by stripping undervacuum at 100° C. for 2 hours.

150 g of such ethyl esters were distilled: the products were collectedfrom 195° to 210° C. and were characterized, on infrared analysis, byabsorption at 1790 cm⁻¹.

These products were then reduced to monofunctional alcohols of formula:

    TO(C.sub.2 F.sub.4 O).sub.n (CF.sub.2 O).sub.m CF.sub.2 CH.sub.2 OH

by means of LiAlH₄, as described above in Example 6.

The products so obtained had a boiling temperature ranging from 175° to190° C.

EXAMPLE 10

A mixture of acids of formula: ##STR34## prepared according to Examples21-23 of Italian patent application No. 20,406 A/88, where T=ClC₃ --, orClCF₂ --, ClC₂ F₄ --, and characterized by average values of m, n and psuch that p/m+n=0.02 and m/n=0.5, a --COOH/T molar ratio=about 1, and anaverage molecular weight of 850, was reacted as in Example 2 in order toobtain the corresponding ethyl ester. 20 g of such ester were dissolvedin 100 cc of a 1/1 by volume solution of ethyl ether and FC 113(1,1,2-trichloro-1,2,2-trifluoroethane) cooled to 0° C.

The solution was subjected to a gaseous ammonia flow for 3 hours. Afterevaporation of the solvent, the residue consisted of a mixture of amidesof formula: ##STR35## as confirmed by the presence of absorption bandsat 1740 cm⁻¹ in the infrared spectrum, where T, n, m and p are the sameas defined hereinbefore.

EXAMPLE 11

10 g of the amides mixture obtained in Example 10 were treated with 20 gof P₂ O₅ at 150°-180° C. for 3 hours. The liquid product obtained fromthe reaction was recovered by distillation and identified as a mixtureof nitriles of formula ##STR36## by infrared analysis (absorption at2250 cm⁻¹).

EXAMPLE 12

50 g of ethyl ester

    ClC.sub.3 F.sub.6 O(C.sub.3 F.sub.6 O).sub.1.27 (CF.sub.2 O).sub.0.05 CF.sub.2 COOC.sub.2 H.sub.5

prepared according to Example 2 were dissolved in 150 cc of a mixture of1,1,2-trichloro-1,2,2-trifluoroethane (FC 113) and methanol in a 1/1weight ratio. Such solution was then additioned with 15 g ofaminopropyltriethoxysilane and then heated at reflux. On conclusion ofthe reaction, the solvent and the reagent in excess were evaporated.

The infrared analysis revealed the disappearance of the ester absorptionband at 1790 cm⁻¹, while the presence of a band at 1740 cm⁻¹characteristic of the amidic group was observable.

The NMR analysis (ISF and 1H) revealed that the product had thefollowing structure: ##STR37##

EXAMPLE 13

A sample of 50 g of a mixture of methylesters prepared according to theprocedure described in Example 20 of Italian patent application No.20,406 A/88, starting from a brominated product obtained according toExample 25 of said application, such esters having formula: ##STR38##where p has an average value of 2.52 and m has an average value of 0.1,and having a molecular weight equal to 800, was added dropwise to asolution of 3.5 g of anhydrous NaBH₄ dissolved in 100 ml of absoluteethyl alcohol, at a temperature around 20° C. On conclusion of dropping(40 minutes), the whole was maintained under stirring at 20° C. for 1hour, then an aqueous solution of hydrochloric acid at 5% was introducedtill a decidedly acid pH was obtained. 80% of the introduced ethylalcohol was distilled off and, after cooling, from the heavy phase therewere obtained, by distillation under vacuum (0.5-1 mm Hg at 90°-110° C.)39 g of an oil which, on infrared analysis, did not exhibit anyabsorption attributable to carbonyl, but a pronounced band in the regionindicating hydroxyls.

By titration with acetic anhydride, as shown in Example 6, an equivalentweight, referred to hydroxyl, equal to 650, corresponding to formula:##STR39## was obtained.

What is claimed is:
 1. A functionalized fluoropolyether defined by theformula (II):

    T'--O (CF.sub.2 CF.sub.2 O).sub.p (CF.sub.2 O).sub.s CRR'Y (II)

where: R is selected from the group consisting of F, Br, I and Cl; R',equal to or different from R, is selected from the group consisting of Fand Cl; T' is selected from the group consisting of

    Alog--CF.sub.2 CF.sub.2 --; Alog--CF.sub.2 --; and Alog CF.sub.2 CF--(Alog)--;

where Alog is Cl; p ranges from 1 to 20, with s/p being between 0.5 and2.0; Y is selected from the group consisting of --CN, --CH₂ Z, --COR'",##STR40## where: E is --NH--, --O-- or --S--, and furthermore with theproviso:(A) when Y is --CH₂ Z, Z is OR", where R" is a hydrogen atom,or: ##STR41## (where b is a number ranging from 1 to 15); ##STR42## (c=anumber from 1 to 3); ##STR43## Where R₁ is an alkyl containing from 1 to30 carbon atoms, with an alkyl containing from 1 to 30 carbon atoms withether bonds of type --C--O--C--, or --(CH₂ --CH₂ O)_(d) H, wherein d isa number ranging from 1 to 15; ##STR44## a naphthyl group; a benzylgroup; or a mono- or poly-substituted alkyl or akoxy benzyl group of thetype: ##STR45## where R₂ =an alkyl containing from 1 to 4 carbon atoms;or Z is a nitrogen-containing group --NR₃ R₄ where R₃ and R₄, alike ordifferent from each other, are hydrogen atoms or they are, eitherindividually or both, R₁ groups as defined above, or, when R₃ =H, R₄ is:##STR46## or R₃ and R₄ together form a cyclic imide of formula:##STR47## wherein the phenyl group contains a substituent group of theanhydride type; ##STR48## (B) and when Y=COR'", R'" , is selected fromthe group consisting of --NHR₅, where R₅ is hydrogen, C₁ -C₈ alkyl, C₁-C₈ mono- or poly-hydroxyalkyl, C₁ -C₈ aminoalkyl, allyl group,methallyl group, R₆ --Si(OCH₃)₃ or R₆ Si(OC₂ H₅)₃, where R₆ is C₁ -C₈alkylene, --R₇ NCO where R₇ is C₁ -C₈ alkylene, C₅ -C₆ cycloalkylene, C₆-C₁₀ arylene, an unsubstituted aromatic radical or a substitutedaromatic radical selected from the group consisting ofpentafluorophenyl, bromotetrafluorophenyl, dibromodifluorophenyl,bromophenyl and bromobenzophenyl.
 2. A functionalized fluoropolyetherdefined by one of the following formulas: ##STR49## where: X is F or CF₃;R is selected from the group consisting of F, Br, I and Cl; R', equalto or different from R, is selected from the group consisting of F, Br,I and Cl; T is a perhaloalkyl group containing from one to three carbonatoms and one or two atoms of Cl; T is selected from the groupconsisting of Alog CF₂ --; Alog ##STR50## and Alog CF₂ CF(CF₃)--; whereAlog is Cl; n ranges from 1 to 15, with m/n being between 0.01 and 0.5;Y is selected from the group consisting of a --CN, --CH₂ Z, --COR'",##STR51## where: E is --NH--, --O-- or --S--, and furthermore with theproviso:(A) when Y=--CH₂ Z, Z is OR", where R" is a hydrogen atom, or:##STR52## --(CH₂ CH₂ O)_(b) H (where b is a number ranging from 1 to15); ##STR53## (c=a number from 1 to 3); ##STR54## where R₁ =an alkylcontaining from 1 to 30 carbon atoms, an alkyl containing ether bonds oftype --C--O--C--, --(CH₂ --CH₂ O)_(n) H, wherein n is a number rangingfrom 1 to 15, a naphthyl group, a benzyl group, or a mono- orpoly-substituted alkyl or alkoxy benzyl group of the type: ##STR55##where R₂ =an alkyl containing from 1 to 4 carbon atoms; or Z is anitrogen-containing group --NR₃ R₄ ; where R₃ and R₄, alike or differentfrom each other, are hydrogen atoms or they are, either individually orboth, R₁ groups as defined above, or, when R₃ =H, R₄ is: ##STR56## or R₃and R₄ together for a cyclic imide of formula: ##STR57## wherein thephenyl group contains a substituent group of the anhydride type;##STR58## (B) when Y=COR'" group, R'" is selected from the groupconsisting of --NHR₅ where R₅ is hydrogen C₁ -C₈ alkyl, C₁ -C₈ mono- orpoly-hydroxyalkyl, C₁ -C₈ aminoalkyl, allyl group, methallyl group, R₆--Si(OCH₃)₃ or R₆ Si(O₂ H₅)₃, where R₆ is C₁ -C₈ alkylene, R₇ NCO, whereR₇ is C₁ -C₈ alkylene, C₅ -C₆ cycloalkylene, C₆ -C₁₀ arylene, anunsubstituted aromatic radical or a substituted aromatic radicalselected from the group consisting of pentafluorophenyl,bromotetrafluorophenyl, dibromodifluorophenyl, bromophenyl andbromobenzophenyl,

    T'--O (CF.sub.2 CF.sub.2 O).sub.p (CF.sub.2 O).sub.s CRR' Y(II)

where: T' is selected from the group consisting of Alog CF₂ CF₂ --, AlogCF₂ -- and Alog CF₂ CF(Alog)--: R, R', Alog and Y are the same asdefined above for formula (I); p ranges from 1 to 20, and s/p rangesfrom 0.5 to 2; and ##STR59## where: Y, X, R and R' are the same asdefined above for formula (I), T" is equal to T or T' o and q areintegers, zero included, o+q ranges from 1 to 20, z/o+q ranges from 0.01to 0.05.